CN108770194A - The preparation method of conductive silver paste used for printed circuit - Google Patents
The preparation method of conductive silver paste used for printed circuit Download PDFInfo
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- CN108770194A CN108770194A CN201810534659.3A CN201810534659A CN108770194A CN 108770194 A CN108770194 A CN 108770194A CN 201810534659 A CN201810534659 A CN 201810534659A CN 108770194 A CN108770194 A CN 108770194A
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- silver paste
- silver powder
- conductive silver
- printed circuit
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Abstract
The invention belongs to conductive silver paste technical fields, and in particular to a kind of preparation method of conductive silver paste used for printed circuit comprising following steps：（1）Prepare required raw material, 10 parts~15 parts of spherical silver powder, 20 parts~30 parts of flake silver powder, 7 parts~10 parts of graphene, 8 parts~12 parts of epoxy modified polyester resin, 10 parts~15 parts of organic solvent, aluminium nitride, antifoaming agent, levelling agent according to parts by weight proportioning；（2）The preparation of organic carrier,（3）It is prepared by conductive silver paste.There is excellent electric conductivity, good adhesive force and bending resistance according to conductive silver paste used for printed circuit made from preparation side provided by the invention.
Description
Technical field
The invention belongs to electronic information material fields, and in particular to a kind of special conductive silver paste of printed circuit and its preparation
Method.
Background technology
Conductive silver paste is widely used in the electronics such as computer, cell phone keyboard, thin film switch, touch screen, smart card, radio frequency identification
Industrial circle, at present the maximum several conductive silver pastes of usage amount include：PET be base material thin film switch and flexible PCB with low
Warm silver paste, touch screen low-temperature conductive silver paste, veneer ceramic capacitor slurry, varistor and thermistor silver paste, pressure
Electroceramics silver paste and carbon-film potentiometer silver electrode paste.It is to aim at resistance-type and capacitive touch screen to print conductive silver paste
The low-temperature bake type conductive silver paste of return wire design, it be made by the splendid silver powder lappingout of high performance resin and electric conductivity and
At suitable on ito film glass.
In capacitive touch screen (English abbreviation：TP) in industry, whole world demand is accepted in domestic capacitive touch screen production
90% or more of amount, wherein internal current export channel overwhelming majority realize that conductive silver paste is that production is each using printing silver paste
The indispensable basic and key function material of kind electronic component products.
Electrocondution slurry is final at can just be obtained through certain curing process again after wet film by the figure silk-screen printing of design
Conductive film layer.Ideal conducting film layer should have there are two key property：First, the geometry and thickness of film layer are strictly controllable；Second is that
The resistance of film layer is as small as possible.In solid character (being free of volatile organic matter), resistance sizes are formed conductive film layer by film layer
In constituent element property influenced, including the volume fraction of binder (resin) and function phase (such as silver powder), pattern, size, point
Cloth and interface etc..Currently, since technique is immature, that there are printing qualities is unstable for existing conductive silver paste, resistance is bigger than normal, not bending resistance
The problems such as folding, poor universality matched with base material.Therefore, improve conductive silver paste electric conductivity, bending resistance and from different bases
The matching of material is the important directions in conductive silver paste research.
China application CN201510483661.9 provides a kind of special conductive yarn printing silver paste of capacitive touch screen, should
The raw material of printing silver paste includes the component of following weight part ratio：60~80 parts of silver powder, 6~10 parts of vinylite, solvent 22
~25 parts, 0.5~3 part of toner, 1~5 part of auxiliary agent, wherein the grain size of the silver powder is 0.0005~0.002mm.It has selected second
Ene based resins and esters solvent, it is ensured that silver powder is uniformly distributed, while also promoting viscosity, and it is good to conform to power, can be compared with after baking
It is bonded on base material well, Gu caking property is good.But the silver paste electric conductivity and existing silver paste are developed without significant difference based on this
The more superior conductive silver paste for touch screens of performance has Important Economic meaning and social value.
Content of the metallic silver in conductive silver paste is directly related with electric conductivity.In a sense, silver-colored content is high,
Electric conductivity to improving it is beneficial, but when its content is more than critical size concentration, electric conductivity can not improve.Contain
For silver content at 80~90% (weight ratio), electric conduction quantity has reached peak, when content continues growing, electrically no longer improves, resistance value
It is in rising trend；When content is less than 60%, the variation of resistance is unstable.In a particular application, silver particles content had been both in silver paste
It to consider stable resistance value, also to be restricted by factors such as curing characteristics, adhesive strength, economy, such as silver particles too high levels,
It is concatenated that the probability that resin is wrapped is low, the bonding force of silver conductor declines after film-forming, the danger for having silver granuel to fall off.Therefore,
The content of silver in current most conductive silver paste is generally 60~70%, and sheet resistance is generally in Ω/ /10 μm 70m or so.Cause
This, there is also the spaces continued to lift up for electric conductivity.
Invention content
The present invention solves the technical problem of：For existing conductive silver paste resistance problem bigger than normal, not resistant to bending, carry
A kind of preparation method of the special conductive silver paste of printed circuit is supplied.
In order to solve the above-mentioned technical problem, one aspect of the present invention provides a kind of preparation side of conductive silver paste used for printed circuit
Method comprising following steps：
(1) prepare required raw material according to following parts by weight proportioning
Spherical silver powder：10 parts~15 parts
Flake silver powder：20 parts~30 parts
Graphene：7 parts~10 parts
Organic carrier epoxy modified polyester resin：8 parts~12 parts
The organic solvent that boiling range is 120 DEG C~180 DEG C：10 parts~15 parts
Aluminium nitride：1 part~2 parts
0.1 part~1 part of antifoaming agent polyether modified siloxane
0.1 part~1 part of levelling agent polyacrylate
0.5 part~1.2 parts of curing agent diaminodiphenylmethane or diamino diphenyl sulfone
Wherein, 0.5 μm~1.5 μm of above-mentioned spherical silver powder diameter, tap density 3g/cm3~5g/cm3, flake silver powder is average
1 μm~2 μm of grain size, tap density 3g/cm3~5g/cm3, graphene grain size is 6nm~8nm, and the organic solvent is cyclohexanone
Or propylene glycol methyl ether acetate, for the epoxy modified polyester resin average molecular weight 50,000~80,000, the aluminium nitride is spherical shape,
Average grain diameter is 50nm~1 μm；
(2) preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 60 DEG C~90 DEG C is heated to, it is complete to be stirred well to resin
Then fully dissolved is maintained in 90 DEG C of thermostat water bath and is kept stirring 4 hours~8 hours, finally cooling obtains viscosity at ambient temperature
For the organic carrier of the centipoise of 8000 centipoises~10000, then antifoaming agent, levelling agent, curing agent and aluminium nitride are sequentially added thereto,
It is thoroughly mixed uniformly；
(3) prepared by conductive silver paste
Spherical silver powder, flake silver powder and graphene are added portionwise, is placed in high speed dispersor and carries out high speed dispersion, is obtained just
Then primary silver paste obtained is added in three-roll grinder and is ground by grade silver paste, and 50 revs/min of fine tuning idler wheel rotating speed~
It 55 revs/min, until fineness tester tests fineness less than 5 μm, after quick agitating and heating, is filtered with polyester net rapidly, i.e.,
Obtain conductive silver paste used for printed circuit.
Further, the preparation method of conductive silver paste used for printed circuit of the present invention comprising,
Prepare required raw material according to following parts by weight proportioning in step (1)
Spherical silver powder：14 parts
Flake silver powder：28 parts
Graphene：10 parts
Organic carrier epoxy modified polyester resin：12 parts
Organic solvent propylene glycol methyl ether acetate：14 parts
Aluminium nitride：1 part
Antifoaming agent polyether modified siloxane：0.7 part
Levelling agent polyacrylate：0.6 part
Curing agent diamino diphenyl sulfone：0.8 part
Wherein, 0.7 μm~1.3 μm of above-mentioned spherical silver powder diameter, tap density 4g/cm3~5g/cm3, flake silver powder is average
1.2 μm~1.8 μm of grain size, tap density 4g/cm3~5g/cm3, graphene grain size is 6nm~8nm, the epoxy-modified polyester
For resin average molecular weight 70,000~80,000, the aluminium nitride is spherical shape, and average grain diameter is 50nm~1 μm；
(2) preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 80 DEG C~90 DEG C is heated to, it is complete to be stirred well to resin
Then fully dissolved is maintained in 90 DEG C of thermostat water bath and is kept stirring 8 hours, the finally cooling viscosity at ambient temperature that obtains is 9000 lis
The organic carrier of~10000 centipoises is moored, then sequentially adds antifoaming agent, levelling agent, curing agent and aluminium nitride thereto, is sufficiently stirred
It is uniformly mixed；
(3) prepared by conductive silver paste
Spherical silver powder, flake silver powder and graphene are added portionwise, is placed in high speed dispersor and carries out high speed dispersion, is obtained just
Then primary silver paste obtained is added in three-roll grinder and is ground by grade silver paste, and 50 revs/min of fine tuning idler wheel rotating speed~
55 revs/min, until fineness tester tests fineness less than 5 μm so that the fineness of conductive silver paste<5 μm, viscosity is 40000 lis
~45000 centipoises are moored, after quick agitating and heating, rapidly with the filtering of 800 mesh polyester nets to get to conductive silver used for printed circuit
Slurry.
On the other hand, the present invention also provides according to conductive silver paste used for printed circuit made from the preparation method.It is described to lead
Electric silver paste it is conductive can, adherence and bending resistance.
Compared with prior art, beneficial effects of the present invention：
First, certain ratio is added in the preparation method of conductive silver paste used for printed circuit of the invention, in used raw material
Example graphene, graphene is a kind of New Two Dimensional carbon material, be one kind by carbon atom with sp2Hybridized orbit forms hexangle type
The flat film of honeycomb lattice has 100 times of electron mobility faster than crystalline silicon, simultaneously with excellent electric conductivity
It also has excellent heat conductivility and excellent mechanical property, these features, it is made to have uniqueness in conductive silver paste application aspect
Advantage, on the one hand can improve the conductive and heat-conductive and mechanical performance of silver paste, while the silver content of silver paste can also be reduced, reduce
Cost；Coordinate spherical silver powder and flake silver powder, to obtain larger bulk density, the mutual contact of the silver powder of two kinds of shapes
Probability is effectively improved, and improves the interface contact state between silver powder and organic carrier, further the shape inside organic carrier
At three-dimensional conductive network structure, and differently shaped particle exists, and the binding site between each component in system can be improved, to
So that system internal bond strength further increases, the presence of flake silver powder can further function as filling and the effect of toughening, from
And improve the electric conductivity and bending resistance of conductive silver paste.
Secondly, in the preparation method of conductive silver paste used for printed circuit of the invention, used organic carrier is selected average
Molecular weight is provided in the active group of 5~80,000 epoxy modified polyester resin modified polyurethane for the polymeric matrix after solidification
Molecular skeleton provides mechanical property and adhesive property guarantee, and conductive filler particles is made to form channel, and cooperation boiling range is 120
~180 DEG C of organic solvent shortens drying time after printed circuit under the conditions of 110~120 DEG C of low-temperature bake, and with it is each
Kind ito thin film and ito glass have excellent combination power, toughness resistant to bending and the good adhesion intensity between base material.
Third, in the preparation method of conductive silver paste used for printed circuit of the invention, organic carrier is complete in resin when preparing
Insulated and stirred after dissolving, it is cooling to obtain the organic carrier that viscosity at ambient temperature is the centipoise of 9000 centipoises~10000, then thereto successively plus
Enter antifoaming agent, levelling agent, curing agent and aluminium nitride, wait for that viscosity reaches the range, auxiliary agent is being added, not only contributes to auxiliary agent hair
The effect of waving can more promote each component to be uniformly mixed；After obtaining organic carrier, by the spherical silver powder of main component, flake silver powder and
Graphene is added portionwise, high speed dispersion, is then ground in three-roll grinder so that the fineness of conductive silver paste<5 μm, viscosity
For the centipoise of 40000 centipoises~45000, after quick agitating and heating, filtering is to get to conductive silver paste used for printed circuit.Pass through control
Fineness, viscosity and filtering make Particle Distribution, contact condition inside conductive silver paste evenly, be more advantageous to the conduction for improving silver paste
Property and the bonding dynamics with base material.
Specific implementation mode
Further detailed description is done to the present invention with reference to specific embodiment, but embodiments of the present invention are not limited to
This.Those skilled in the art will realize that：Chemical reaction described in the invention can be used for suitably preparing many
Other compounds of invention are used to prepare the chemical combination of the present invention for example, making some conventional modifications according to reaction condition of the present invention
Other methods of object are considered as within the scope of the present invention.
Spherical silver powder and flake silver powder used in the embodiment of the present invention are purchased from Guiyan Platium Co., Ltd, stone
Black alkene is purchased from Shandong Jin Cheng graphenes Science and Technology Ltd., other do not indicate reagent such as epoxy modified polyester resin, two of producer
Diaminodiphenylmethane, diamino diphenyl sulfone and the unlimited producer of organic solvent cyclohexanone, propylene glycol methyl ether acetate.
Embodiment 1：
Step (1) prepares required raw material according to following parts by weight proportioning
0.7 μm~1.3 μm of grain size, tap density 4g/cm3~5g/cm3Spherical silver powder：140g
1.2 μm~1.8 μm of average grain diameter, tap density 4g/cm3~5g/cm3Flake silver powder：280g
Grain size is the graphene of 6nm~8nm：100g
Epoxy modified polyester resin of the average molecular weight 70,000~80,000：120g
Propylene glycol methyl ether acetate：140g
Average grain diameter is the spherical aluminum nitride of 50nm~1 μm：10g
Antifoaming agent polyether modified siloxane：7g
Levelling agent polyacrylate：6g
Curing agent diamino diphenyl sulfone：8g.
A certain proportion of graphene is added in raw material used in formula, graphene is a kind of New Two Dimensional carbon material,
Be one kind by carbon atom with sp2Hybridized orbit forms the flat film that hexangle type is in honeycomb lattice, with excellent electric conductivity
Can, there is 100 times of electron mobility faster than crystalline silicon, while it also has excellent heat conductivility and excellent mechanical property,
These features, make its conductive silver paste application aspect have unique advantage, on the one hand can improve silver paste conductive and heat-conductive and
Mechanical performance, while the silver content of silver paste can also be reduced, reduce cost；Coordinate spherical silver powder and flake silver powder, to obtain
Larger bulk density, the contact probability that the silver powder of two kinds of shapes is mutual are effectively improved, and silver powder and organic carrier are improved
Between interface contact state, three-dimensional conductive network structure, and differently shaped particle are further formed inside organic carrier
In the presence of, the binding site between each component in system can be improved, so that system internal bond strength further increases, sheet
The presence of silver powder can further function as filling and the effect of toughening, to improve the electric conductivity and bending resistance of conductive silver paste
Energy.
Organic carrier select average molecular weight 5~80,000 epoxy modified polyester resin modified polyurethane active group
Molecular skeleton is provided for the polymeric matrix after solidification, provides mechanical property and adhesive property guarantee, and makes conductive filler grain
Son forms channel, and cooperation boiling range is 120~180 DEG C of organic solvent, in 110~120 DEG C of low-temperature bake item after printed circuit
Under part, shorten drying time, and with various ito thin films and ito glass has excellent combination power, toughness resistant to bending and between base material
Good adhesion intensity.
(2) preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 80 DEG C~90 DEG C is heated to, it is complete to be stirred well to resin
Then fully dissolved is maintained in 90 DEG C of thermostat water bath and is kept stirring 6 hours, the finally cooling viscosity at ambient temperature that obtains is 9000 lis
The organic carrier of~10000 centipoises is moored, then sequentially adds polyether modified siloxane, polyacrylate, diamino hexichol thereto
Base sulfone and aluminium nitride are thoroughly mixed uniformly.
(3) prepared by conductive silver paste
Spherical silver powder, flake silver powder and graphene are added in three batches, is placed in high speed dispersor and carries out high speed dispersion, obtain
Then primary silver paste obtained is added in three-roll grinder and is ground by primary silver paste, 50 revs/min of fine tuning idler wheel rotating speed
~55 revs/min, until fineness tester tests fineness less than 5 μm so that the fineness of conductive silver paste<5 μm, viscosity 40000
The centipoise of centipoise~45000, after quick agitating and heating, rapidly with the filtering of 800 mesh polyester nets to get to conductive silver used for printed circuit
Slurry.
When organic carrier is prepared after resin is completely dissolved insulated and stirred, it is cooling obtain viscosity at ambient temperature be 9000 centipoises~
The organic carrier of 10000 centipoises, then antifoaming agent, levelling agent, curing agent and aluminium nitride are sequentially added thereto, wait for that viscosity reaches institute
Range is stated, auxiliary agent is being added, is not only contributing to auxiliary agent and plays a role, each component can more be promoted to be uniformly mixed；It has obtained airborne
After body, the spherical silver powder of main component, flake silver powder and graphene are added portionwise, high speed dispersion, then in three-roll grinder into
Row grinding so that the fineness of conductive silver paste<5 μm, viscosity is the centipoise of 40000 centipoises~45000, after quick agitating and heating, filtering,
Obtain conductive silver paste used for printed circuit.
By controlling fineness, viscosity and filtering, make conductive silver paste inside Particle Distribution, contact condition evenly, more favorably
In improve silver paste electric conductivity and with the bonding dynamics of base material.And silver paste fineness is smaller to be more conducive to the parallel silver wire of printing microspur,
Such as wide 0.05mm, at a distance of the parallel silver wire of 0.1mm.
Embodiment 2：
(1) prepare required raw material according to following parts by weight proportioning
Step (1) prepares required raw material according to following parts by weight proportioning
0.5 μm~1.0 μm of grain size, tap density 4g/cm3~5g/cm3Spherical silver powder：100g
1.0 μm~1.5 μm of average grain diameter, tap density 4g/cm3~5g/cm3Flake silver powder：200g
Grain size is the graphene of 6nm~8nm：100g
Epoxy modified polyester resin of the average molecular weight 50,000~70,000：120g
Propylene glycol methyl ether acetate：100g
Average grain diameter is the spherical aluminum nitride of 50nm~1 μm：20g
Antifoaming agent polyether modified siloxane：1g
Levelling agent polyacrylate：1g
Curing agent diamino diphenyl sulfone：5g.
(2) preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 70 DEG C~80 DEG C is heated to, it is complete to be stirred well to resin
Then fully dissolved is maintained in 90 DEG C of thermostat water bath and is kept stirring 8 hours, the finally cooling viscosity at ambient temperature that obtains is 8000 lis
The organic carrier of~9000 centipoises is moored, then sequentially adds polyether modified siloxane, polyacrylate, diamino-diphenyl thereto
Sulfone and aluminium nitride are thoroughly mixed uniformly.
(3) prepared by conductive silver paste
Spherical silver powder, flake silver powder and graphene are added portionwise, is placed in high speed dispersor and carries out high speed dispersion, is obtained just
Then primary silver paste obtained is added in three-roll grinder and is ground by grade silver paste, and 50 revs/min of fine tuning idler wheel rotating speed~
55 revs/min, fineness tester is tested until fineness is less than 5 μm, and viscosity is the centipoise of 40000 centipoises~45000, quickly stirring plus
After heat, rapidly with the filtering of 800 mesh polyester nets to get to conductive silver paste used for printed circuit.
Embodiment 3：
(1) prepare required raw material according to following parts by weight proportioning
Step (1) prepares required raw material according to following parts by weight proportioning
1.0 μm~1.5 μm of grain size, tap density 3g/cm3~4g/cm3Spherical silver powder：150g
1.5 μm~2.0 μm of average grain diameter, tap density 3g/cm3~4g/cm3Flake silver powder：300g
Grain size is the graphene of 6nm~8nm：70g
Epoxy modified polyester resin of the average molecular weight 50,000~60,000：80g
Propylene glycol methyl ether acetate：150g
Average grain diameter is the spherical aluminum nitride of 50nm~1 μm：12g
Antifoaming agent polyether modified siloxane：6g
Levelling agent polyacrylate：7g
Curing agent diaminodiphenylmethane：12g.
(2) preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 70 DEG C~80 DEG C is heated to, it is complete to be stirred well to resin
Then fully dissolved is maintained in 90 DEG C of thermostat water bath and is kept stirring 4 hours, the finally cooling viscosity at ambient temperature that obtains is 8000 lis
The organic carrier of~9000 centipoises is moored, then sequentially adds polyether modified siloxane, polyacrylate, diamino hexichol first thereto
Alkane and aluminium nitride are thoroughly mixed uniformly.
(3) prepared by conductive silver paste
Spherical silver powder, flake silver powder and graphene are added portionwise, is placed in high speed dispersor and carries out high speed dispersion, is obtained just
Then primary silver paste obtained is added in three-roll grinder and is ground by grade silver paste, and 50 revs/min of fine tuning idler wheel rotating speed~
55 revs/min, fineness tester is tested until fineness is less than 5 μm, and viscosity is the centipoise of 40000 centipoises~45000, quickly stirring plus
After heat, rapidly with the filtering of 800 mesh polyester nets to get to conductive silver paste used for printed circuit.
Embodiment 4：
(1) prepare required raw material according to following parts by weight proportioning
Step (1) prepares required raw material according to following parts by weight proportioning
0.5 μm~1.0 μm of grain size, tap density 4g/cm3~5g/cm3Spherical silver powder：130g
1.0 μm~1.5 μm of average grain diameter, tap density 4g/cm3~5g/cm3Flake silver powder：250g
Grain size is the graphene of 6nm~8nm：80g
Epoxy modified polyester resin of the average molecular weight 70,000~80,000：100g
Propylene glycol methyl ether acetate：120g
Average grain diameter is the spherical aluminum nitride of 50nm~1 μm：10g
Antifoaming agent polyether modified siloxane：10g
Levelling agent polyacrylate：10g
Curing agent diamino diphenyl sulfone：8g.
(2) preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 80 DEG C~90 DEG C is heated to, it is complete to be stirred well to resin
Then fully dissolved is maintained in 90 DEG C of thermostat water bath and is kept stirring 8 hours, the finally cooling viscosity at ambient temperature that obtains is 8000 lis
The organic carrier of~9000 centipoises is moored, then sequentially adds polyether modified siloxane, polyacrylate, diamino-diphenyl thereto
Sulfone and aluminium nitride are thoroughly mixed uniformly.
(3) prepared by conductive silver paste
Spherical silver powder, flake silver powder and graphene are added portionwise, is placed in high speed dispersor and carries out high speed dispersion, is obtained just
Then primary silver paste obtained is added in three-roll grinder and is ground by grade silver paste, and 50 revs/min of fine tuning idler wheel rotating speed~
55 revs/min, fineness tester is tested until fineness is less than 5 μm, and viscosity is the centipoise of 40000 centipoises~45000, quickly stirring plus
After heat, rapidly with the filtering of 800 mesh polyester nets to get to conductive silver paste used for printed circuit.
Embodiment 5：
(1) prepare required raw material according to following parts by weight proportioning
Step (1) prepares required raw material according to following parts by weight proportioning
1.0 μm~1.5 μm of average grain diameter, tap density 3g/cm3~4g/cm3Flake silver powder：280g
Grain size is the graphene of 6nm~8nm：100g
Epoxy modified polyester resin of the average molecular weight 50,000~60,000：120g
Propylene glycol methyl ether acetate：140g
Average grain diameter is the spherical aluminum nitride of 50nm~1 μm：10g
Antifoaming agent polyether modified siloxane：8g
Levelling agent polyacrylate：8g
Curing agent diamino diphenyl sulfone：8g.
(2) preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 80 DEG C~90 DEG C is heated to, it is complete to be stirred well to resin
Then fully dissolved is maintained in 90 DEG C of thermostat water bath and is kept stirring 8 hours, the finally cooling viscosity at ambient temperature that obtains is 8000 lis
The organic carrier of~9000 centipoises is moored, then sequentially adds polyether modified siloxane, polyacrylate, diamino-diphenyl thereto
Sulfone and aluminium nitride are thoroughly mixed uniformly.
(3) prepared by conductive silver paste
Graphene and flake silver powder are added portionwise, is placed in high speed dispersor and carries out high speed dispersion, obtains primary silver paste, so
Primary silver paste obtained is added in three-roll grinder afterwards and is ground, 50 revs/min~55 revs/min of fine tuning idler wheel rotating speed
Clock, fineness tester are tested until fineness is less than 5 μm, and viscosity is the centipoise of 40000 centipoises~45000, fast after quick agitating and heating
Speed is with the filtering of 800 mesh polyester nets to get to conductive silver paste used for printed circuit.
Embodiment 6：
(1) prepare required raw material according to following parts by weight proportioning
Step (1) prepares required raw material according to following parts by weight proportioning
0.5 μm~1.0 μm of grain size, tap density 4g/cm3~5g/cm3Spherical silver powder：140g
1.0 μm~1.5 μm of average grain diameter, tap density 3g/cm3~4g/cm3Flake silver powder：280g
Epoxy modified polyester resin of the average molecular weight 50,000~60,000：120g
Propylene glycol methyl ether acetate：140g
Average grain diameter is the spherical aluminum nitride of 50nm~1 μm：10g
Antifoaming agent polyether modified siloxane：8g
Levelling agent polyacrylate：8g
Curing agent diamino diphenyl sulfone：8g.
(2) preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 80 DEG C~90 DEG C is heated to, it is complete to be stirred well to resin
Then fully dissolved is maintained in 90 DEG C of thermostat water bath and is kept stirring 8 hours, the finally cooling viscosity at ambient temperature that obtains is 8000 lis
The organic carrier of~9000 centipoises is moored, then sequentially adds polyether modified siloxane, polyacrylate, diamino-diphenyl thereto
Sulfone and aluminium nitride are thoroughly mixed uniformly.
(3) prepared by conductive silver paste
Spherical silver powder and flake silver powder are added portionwise, is placed in high speed dispersor and carries out high speed dispersion, obtains primary silver paste,
Then primary silver paste obtained is added in three-roll grinder and is ground, 50 revs/min~55 revs/min of fine tuning idler wheel rotating speed
Clock, fineness tester are tested until fineness is less than 5 μm, and viscosity is the centipoise of 40000 centipoises~45000, fast after quick agitating and heating
Speed is with the filtering of 800 mesh polyester nets to get to conductive silver paste used for printed circuit.
Embodiment 7：
(1) prepare required raw material according to following parts by weight proportioning
Step (1) prepares required raw material according to following parts by weight proportioning
0.5 μm~1.0 μm of grain size, tap density 4g/cm3~5g/cm3Spherical silver powder：140g
1.0 μm~1.5 μm of average grain diameter, tap density 3g/cm3~4g/cm3Flake silver powder：280g
Grain size is the graphene of 6nm~8nm：100g
Epoxy modified polyester resin of the average molecular weight 50,000：120g
Propylene glycol methyl ether acetate：140g
Antifoaming agent polyether modified siloxane：8g
Levelling agent polyacrylate：8g
Curing agent diamino diphenyl sulfone：8g.
(2) preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 80 DEG C~90 DEG C is heated to, it is complete to be stirred well to resin
Then fully dissolved is maintained in 90 DEG C of thermostat water bath and is kept stirring 8 hours, the finally cooling viscosity at ambient temperature that obtains is 8000 lis
The organic carrier of~9000 centipoises is moored, then sequentially adds polyether modified siloxane, polyacrylate and diamino hexichol thereto
Base sulfone is thoroughly mixed uniformly.
(3) prepared by conductive silver paste
Spherical silver powder, flake silver powder and graphene are added portionwise, is placed in high speed dispersor and carries out high speed dispersion, is obtained just
Then primary silver paste obtained is added in three-roll grinder and is ground by grade silver paste, and 50 revs/min of fine tuning idler wheel rotating speed~
55 revs/min, fineness tester is tested until fineness is less than 5 μm, and viscosity is the centipoise of 40000 centipoises~45000, quickly stirring plus
After heat, rapidly with the filtering of 800 mesh polyester nets to get to conductive silver paste used for printed circuit.
Embodiment 8：
(1) prepare required raw material according to following parts by weight proportioning
Step (1) prepares required raw material according to following parts by weight proportioning
0.5 μm~1.0 μm of grain size, tap density 4g/cm3~5g/cm3Spherical silver powder：140g
1.0 μm~1.5 μm of average grain diameter, tap density 3g/cm3~4g/cm3Flake silver powder：280g
Grain size is the graphene of 6nm~8nm：100g
Epoxy modified polyester resin of the average molecular weight 20,000~30,000：120g
Propylene glycol methyl ether acetate：140g
Average grain diameter is the spherical aluminum nitride of 50nm~1 μm：10g
Antifoaming agent polyether modified siloxane：8g
Levelling agent polyacrylate：8g
Curing agent diamino diphenyl sulfone：8g.
(2) preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 80 DEG C~90 DEG C is heated to, it is complete to be stirred well to resin
Then fully dissolved is maintained in 90 DEG C of thermostat water bath and is kept stirring 8 hours, the finally cooling viscosity at ambient temperature that obtains is 8000 lis
The organic carrier of~9000 centipoises is moored, then sequentially adds polyether modified siloxane, polyacrylate, diamino-diphenyl thereto
Sulfone and aluminium nitride are thoroughly mixed uniformly.
(3) prepared by conductive silver paste
Spherical silver powder and flake silver powder are added portionwise, is placed in high speed dispersor and carries out high speed dispersion, obtains primary silver paste,
Then primary silver paste obtained is added in three-roll grinder and is ground, 50 revs/min~55 revs/min of fine tuning idler wheel rotating speed
Clock, fineness tester are tested until fineness is less than 5 μm, and viscosity is the centipoise of 40000 centipoises~45000, fast after quick agitating and heating
Speed is with the filtering of 800 mesh polyester nets to get to conductive silver paste used for printed circuit.
The conductive silver paste that the embodiment of the present invention 1~8 prepares gained is printed using the polyester net of 800 mesh in semi-automatic screen
On the ITO/PET films of machine, silk-screen fine conductive circuit.Wherein, the fine conductive circuit of silk-screen be five serpentines, line width/
Line-spacing is followed successively by 50 μm/50 μm, 60 μm/60 μm, 70 μm/70 μm, 80 μm/80 μm, 100 μm/100 μm, and thickness is 2 μm~6 μm；
At 130 DEG C, baking after sixty minutes, is observed under the microscope, the conducting wire surfacing of 50 μm and above line width/line-spacing, edge
It is clear smooth.
Performance test embodiment：
Comparative example：The conductive silver paste of Shanghai Electron Material Co., Ltd production.
The conductive silver paste used for printed circuit of 1 to 7 gained of example and comparative example product are used into same way silk-screen, dried,
Then performance detection is carried out, specific detection method is as follows：
1. sheet resistance：Then the resistance value that printed conductor is tested out using digital multi-purpose electric meter calculates sheet resistance, m Ω/.
2. bending resistance is tested：Printed conductor is bent 180 ° to external symmetry, and is pressed in silver paste using counterweight, pressure
About 5.5kPa keeps 1min；It again by 180 ° of the reversed doubling of printed conductor, is pressed in silver paste using same counterweight, keeps 1min,
Carry out the conductivity test of silver paste.Above step is considered as 1 crooked test, repeats above operation until conductor cord disconnection (test time
Number≤10 times).
3. viscosity test：NDJ-1 rotational viscometers, 5rpm, 25 DEG C, Pa.S.
4. fineness：Hegman grind gage, μm.
5. adhesive force：(ITO/PT films) is tested using hundred lattice of national regulations, 600 adhesive tapes of 3M are vertical to draw, ASTM standard.
6. hardness：Pencil hardness, H.
7. thermal ageing test：60 DEG C, 240 hours.
8. moisture-proof is tested：60 DEG C, 85%, 240 hour.
9. low temperature resistant loop test：- 20~40 DEG C, 10 cycles.
10. operating temperature (DEG C)：Circuit.
Specific testing result is shown in Tables 1 and 2.
Table 1：Performance test results one
By 1 testing result of table it is found that conductive silver paste used for printed circuit prepared by technical solution of the present invention is improving electric conductivity
While can be with adhesive force, buckle resistance can be significantly improved also, developed to it and applied with facilitation.
According to the performance test results of the testing result of Examples 1 to 4 and embodiment 5~8, it can be found that working as conductive silver paste
Only use flake silver powder and graphene cooperation as conductive material when, printed circuit sheet resistance compared with existing commercially available conductive silver paste,
It decreases.When conductive silver paste only uses flake silver powder and spherical silver powder, when without adding graphene, printed circuit sheet resistance with it is existing
Commercially available conductive silver paste is compared, and no reduction, the experimental result is shown, the addition of graphene has important work for reducing sheet resistance
With.
Selection for organic carrier after having tried out different resins, has selected epoxy modified polyester resin, conduction can be improved
The mechanical property and adhesive property of silver paste find the molecular weight of resin by further studying (embodiment 8 and Examples 1 to 4)
There is apparent influence for performance, the epoxy modified polyester resin using the low molecular weight of the degree of polymerization less than or equal to 30,000 is made
Conductive silver paste attachment dynamics is more preferable not as good as the resin effect of molecular weight 50,000~80,000, and bending resistance is also be not as moderate as the degree of polymerization
Conductive silver paste is made in resin.
Comparative example
Table 2：Performance test results two
By 2 testing result of table it is found that the conductive silver paste used for printed circuit for preparing of technical solution of the present invention is in heat ageing, resistance to low
Temperature cycle and corrosion resistance aspect of performance are also superior to high-end product in the market or suitable with high-end product on existing market.
According to the performance test results of the testing result of Examples 1 to 4 and embodiment 7, it can be found that working as conductive silver paste not
When using aluminium nitride, thermal ageing test and operating temperature performance can deteriorate.Aluminium nitride has super-strong high temperature-resistant and high heat conduction two
The heat resistance and operating temperature of silver paste can be improved in big characteristic.Meanwhile comparative example 6 can find that graphene is excellent with embodiment 5
Heat conductivility more also has certain positive phase separation for the heat aging performance and operating temperature that promote printed circuit.
In summary the performance test results, according to the more excellent preparation method of the present invention by improving composition of raw materials and preparing work
Skill, final prepared conductive silver paste sheet resistance used for printed circuit is low, bending resistance is superior, heat ageing, low temperature resistant cycle and resistance to
Corrosion performance is also at industry advanced level.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
The specific implementation of the present invention is confined to these explanations.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the present invention's
Protection domain.
Claims (3)
1. the preparation method of conductive silver paste used for printed circuit comprising following steps：
（1）Prepare required raw material according to following parts by weight proportioning
Spherical silver powder：10 parts~15 parts
Flake silver powder：20 parts~30 parts
Graphene：7 parts~10 parts
Organic carrier epoxy modified polyester resin：8 parts~12 parts
The organic solvent that boiling range is 120 DEG C~180 DEG C：10 parts~15 parts
Aluminium nitride：1 part ~ 2 parts
0.1 part~1 part of antifoaming agent polyether modified siloxane
0.1 part~1 part of levelling agent polyacrylate
0.5 part~1.2 parts of curing agent diaminodiphenylmethane or diamino diphenyl sulfone,
Wherein, 0.5 μm~1.5 μm of above-mentioned spherical silver powder diameter, tap density 3g/cm3~5g/cm3, flake silver powder average grain diameter 1
μm~2 μm, tap density 3g/cm3~5g/cm3, graphene grain size is 6nm~8nm, and the organic solvent is cyclohexanone or the third two
Alcohol methyl ether acetate, for the epoxy modified polyester resin average molecular weight 50,000 ~ 80,000, the aluminium nitride is spherical shape, average grain
Diameter is 50 nm ~ 1 μm；
（2）The preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 60 DEG C~90 DEG C is heated to, it is completely molten to be stirred well to resin
Then solution is maintained in 90 DEG C of thermostat water bath and is kept stirring 4 hours~8 hours, finally cooling obtains viscosity at ambient temperature and is
The organic carrier of the centipoise of 8000 centipoises~10000, then antifoaming agent, levelling agent, curing agent and aluminium nitride are sequentially added thereto, it fills
Divide and is uniformly mixed；
（3）It is prepared by conductive silver paste
Spherical silver powder, flake silver powder and graphene are added portionwise, is placed in high speed dispersor and carries out high speed dispersion, obtains primary silver
Then primary silver paste obtained is added in three-roll grinder and is ground by slurry, fine tuning idler wheel rotating speed 50 revs/min~55
Rev/min, fineness tester test fineness be less than 5 μm until, after quick agitating and heating, rapidly with polyester net filter to get
To conductive silver paste used for printed circuit.
2. the preparation method of conductive silver paste used for printed circuit according to claim 1, which is characterized in that
Step（1）According to following parts by weight proportioning prepare needed for raw material
Spherical silver powder：14 parts
Flake silver powder：28 parts
Graphene：10 parts
Organic carrier epoxy modified polyester resin：12 parts
Organic solvent propylene glycol methyl ether acetate：14 parts
Aluminium nitride：1 part
Antifoaming agent polyether modified siloxane：0.7 part
Levelling agent polyacrylate：0.6 part
Curing agent diamino diphenyl sulfone：0.8 part
Wherein, 0.7 μm~1.3 μm of above-mentioned spherical silver powder diameter, tap density 4g/cm3~5g/cm3, flake silver powder average grain diameter
1.2 μm~1.8 μm, tap density 4g/cm3~5g/cm3, graphene grain size is 6nm~8nm, the epoxy modified polyester resin
For average molecular weight 70,000 ~ 80,000, the aluminium nitride is spherical shape, and average grain diameter is 50 nm ~ 1 μm；
（2）The preparation of organic carrier
Epoxy modified polyester resin is added in organic solvent, 80 DEG C~90 DEG C is heated to, it is completely molten to be stirred well to resin
Then solution is maintained in 90 DEG C of thermostat water bath and is kept stirring 8 hours, the finally cooling viscosity at ambient temperature that obtains is 9000 centipoises
The organic carrier of~10000 centipoises, then antifoaming agent, levelling agent, curing agent and aluminium nitride are sequentially added thereto, it is sufficiently stirred mixed
It closes uniform；
（3）It is prepared by conductive silver paste
Spherical silver powder, flake silver powder and graphene are added portionwise, is placed in high speed dispersor and carries out high speed dispersion, obtains primary silver
Then primary silver paste obtained is added in three-roll grinder and is ground by slurry, fine tuning idler wheel rotating speed 50 revs/min~55
Rev/min, until fineness tester tests fineness less than 5 μm so that the fineness of conductive silver paste<5 μm, viscosity is 40000 centipoises
~45000 centipoises, after quick agitating and heating, rapidly with the filtering of 800 mesh polyester nets to get to conductive silver paste used for printed circuit.
3. one kind is according to conductive silver paste used for printed circuit made from preparation method described in claims 1 or 2.
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| CN112793259A (en) * | 2021-04-12 | 2021-05-14 | 广东南亮艺术玻璃科技股份有限公司 | Heat-conducting glass and preparation method thereof |
| CN112908513A (en) * | 2021-01-20 | 2021-06-04 | 深圳市哈深智材科技有限公司 | Conductive silver paste for flexible circuit and preparation method thereof |
| CN115732117A (en) * | 2022-03-08 | 2023-03-03 | 重庆恩辰新材料科技有限责任公司 | Conductive silver paste for ceramic surface circuit printing and preparation method and application thereof |
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| CN115732117B (en) * | 2022-03-08 | 2024-01-19 | 重庆恩辰新材料科技有限责任公司 | Conductive silver paste for ceramic surface circuit printing and preparation method and application thereof |
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